WO2013137101A1 - Laminated film and method for producing same - Google Patents

Laminated film and method for producing same Download PDF

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Publication number
WO2013137101A1
WO2013137101A1 PCT/JP2013/056292 JP2013056292W WO2013137101A1 WO 2013137101 A1 WO2013137101 A1 WO 2013137101A1 JP 2013056292 W JP2013056292 W JP 2013056292W WO 2013137101 A1 WO2013137101 A1 WO 2013137101A1
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WO
WIPO (PCT)
Prior art keywords
resin
formula
group
oxide particles
laminated film
Prior art date
Application number
PCT/JP2013/056292
Other languages
French (fr)
Japanese (ja)
Inventor
阿部悠
尾形雅美
高田育
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2012059722 priority Critical
Priority to JP2012-059722 priority
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Publication of WO2013137101A1 publication Critical patent/WO2013137101A1/en

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    • C09D167/03Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797Next to addition polymer from unsaturated monomers
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31935Ester, halide or nitrile of addition polymer

Abstract

Provided is a laminated film in which a resin layer is disposed on at least one side of a polyester film. The resin layer comprises at least metal oxide particles (A) having a number-average particle diameter of 3 nm to 50 nm inclusive, acrylic resin (B), and component (C1) derived from an oxazoline compound and/or component (C2) derived from a melamine compound. The acrylic resin (B) is a resin having monomer units (b1), monomer units (b2), and monomer units (b3). Provided at a low-cost is the laminated film that has excellent transparency, suppression of interference spots when a hard coating layer having a high refractive index is laminated, adhesiveness with a hard coating layer having a high refractive index, and adhesiveness under high temperatures and high humidity (moist heat adhesiveness).

Description

Laminate film and manufacturing method thereof

The present invention relates to a laminated film resin layer is provided on at least one side of the polyester film. More particularly, transparency, suppression of interference spots at the time of laminating a high refractive index hard coat layer (visibility), adhesion between the high refractive index hard coat layer, adhesion under high temperature and high humidity (wet heat adhesive property) on the excellent laminated film.

Thermoplastic resin films, biaxially oriented polyester film among others, mechanical properties, electrical properties, dimensional stability, transparency, because of its excellent properties such as chemical resistance, magnetic recording material, the number of such packaging materials It is widely used in applications.

Polyester film, especially in recent years, a touch panel, a liquid crystal display panel (LCD), plasma display panel (PDP), an organic electroluminescence (organic EL), including display member applications etc., are used in various optical films.

Particularly in such applications, the hard coat film hard coat layer is laminated onto a polyester film is used. In order to improve the adhesion between the polyester film and the hard coat layer is a substrate, as these intermediate layers are often coated layer having an easy adhesion property is provided.

The hard coat film, room temperature, more adhesion to the substrate under high temperature and high humidity, transparency, scratch resistance, etc. antifouling property are required. Further, since it is often used for the surface of the display, visibility and design property are required to have hard coat film. Case of laminating a hard coat layer on a polyester film as a base material, since it is when the refractive index of the polyester film is a hard coat layer and the base material are different cause interference spots by interfacial reflection, visibility is deteriorated , reduction of interference spots are being sought. Therefore, the refractive index adjusting layer on the hard coat layer (AR layer, the index-matching layer) and, even after forming the antifouling layer, or if the visibility such as the image display device is deteriorated, if the luxury is impaired there is.

In recent years, further larger screens, higher resolution, with the higher reduction, in particular the suppression of interference spots of a fluorescent lamp, transparency, been increasing demand levels for adhesion between the layers.

On the other hand, the hard coat layer surface, the case of laminating a refractive index adjustment layer composed of a high refractive index layer / low refractive index layer, by a high refractive index of the hard coat layer, high refractive from refractive index adjusting layer it can be omitted rate layer. As a result, in the manufacturing process of the film, without impairing the function, it is possible to greatly reduce the cost. This technique for recent years of strong cost reduction request has been attracting attention.

If provided with such a high refractive index hard coat layer (e.g., a refractive index 1.63) on a polyester film base (e.g. refractive index 1.66), as a method of suppressing interference spots, (a) after forming the adhesive layer, subjected to calender treatment to a substrate film, a method of reducing the localized variation in thickness of the substrate film is disclosed (Patent Document 1).

Also, disclosed is a method of utilizing the cancellation surface to the low refractive index layer is provided, the adhesive layer is provided having an intermediate refractive index of the hard coat layer and the substrate film, interference (b) base film and that (Patent Document 2).

Further, during (c) a hard coat layer and the substrate film, provided with a high refractive index readily adhesive layer of which has a refractive index of their middle a (1.63 to 1.66) method (Patent Documents 3 and 4) , metal oxide particles having a high refractive index, an average particle diameter in combination with 200nm or more coarse particles process for forming an uneven structure at the interface of the coating layer and the hard coat layer is disclosed (Patent Document 5) .
JP 2001-71439 JP Patent No. 4169548 Publication Patent No. 3632044 Publication JP 2004-54161 JP Patent No. 4547644

In the method of Patent Document 1, although the refractive index of the hard coat layer can be relatively interference spots is suppressed in the case of 1.60 or less, the case of laminating the hard coat layer of 1.60 or more 1.65 or less, although adhesion good, interference spots were those noticeable.

Further, the method of Patent Document 2, the material of the substrate was achieved, it lacks versatility such as applying is limited to the case of polyethylene naphthalene dicarboxylate (refractive index 1.7 or higher).

The method in Patent Documents 3 and 4, respectively, the method of adding the water-soluble metal chelate compound or a metal acylate compound water-soluble polyester resin (Patent Document 3), the addition of metal oxides of the polymer binder and a high refractive index ( Patent Document 4) it has been proposed. However, it is necessary to add a large amount of fine particles of nano-order, in the case of using fine particles of nano-order, and aggregating the surface area of ​​the fine particles increases dramatically, transparency was a problem to decrease. The fine particles becomes refractive index nonuniformity in the plane of the aggregated resin layer, even the suppression of interference spots there is a problem to decrease. Further, in the resin layer, in the portion where fine particles are aggregated, to the ratio is relatively decreased contributing binder component adhesiveness to the hard coat layer, there is a problem that adhesiveness lowers.

In Patent Document 5, a metal oxide particle with an average particle diameter 200nm or more coarse particles utilizing light scattering by an average particle diameter 200nm or more coarse particles thereby reducing the interference spots. In this case, since the use of light scattering, there is a problem that the haze of the coating film increases.

Therefore, in the present invention to eliminate the above drawbacks, transparency, visibility, and to provide a superior laminated polyester film adhesion to the substrate and the hard coat layer.

The laminated film of the present invention for solving the above problems has one of the following configurations:. That is,
A laminated film resin layer is provided on at least one side of the polyester film, the resin layer includes a number-average particle diameter of 3nm or more 50nm or less of the metal oxide particles (A), an acrylic resin (B), oxazoline system compound (C 1 ') and / or the melamine compound (C 2') contains at least, the acrylic resin (B), and monomer units (b 1) of the formula (1), formula (2 a monomer unit (b 2) represented by), the laminated film is a resin having a monomer unit represented by formula (3) (b 3),
Or,
A laminated film resin layer is provided on at least one side of the polyester film, the resin layer includes a number-average particle diameter of 3nm or more 50nm or less of the metal oxide particles (A), an acrylic resin (B), oxazoline system compound derived from components (C 1) and / or components derived from melamine compound (C 2) contains at least, the acrylic resin (B), monomer units (b 1 represented by the formula (1) ) and, as a monomer unit (b 2) represented by the formula (2) is a laminated film, a resin having a monomer unit (b 3) represented by the formula (3).

Figure JPOXMLDOC01-appb-C000013

(In formula (1), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.)

Figure JPOXMLDOC01-appb-C000014

(Formula (In 2), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)

Figure JPOXMLDOC01-appb-C000015

In (formula (3), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
In the method of manufacturing the laminated film of the present invention has the following configuration. That is,
And at least manufacturing method of a multilayer film on one side to provide a resin layer of a polyester film, on at least one side of a polyester film, allowed to form a resin with the following resin composition and then, stretching the laminated film at least in a uniaxial direction and, then, a method of manufacturing a multilayer film, wherein the heat treatment to the laminated film is.

Here, the resin composition has a number-average particle diameter of 3nm or more 50nm or less of the metal oxide particles (A), an acrylic resin (B), oxazoline compound (C 1 ') and / or the melamine compound ( C 2 ') to be at least a resin composition containing, the acrylic resin (B), the equation (1) a monomer unit represented by (b 1), a monomer represented by the formula (2) units ( and b 2), a resin having a monomer unit represented by formula (3) (b 3).

Figure JPOXMLDOC01-appb-C000016

(In formula (1), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.)

Figure JPOXMLDOC01-appb-C000017

(Formula (In 2), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)

Figure JPOXMLDOC01-appb-C000018

In (formula (3), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.).

The laminated film of the present invention, transparency, the suppression of interference spots at the time of laminating a high refractive index hard coat layer, adhesion between the high refractive index hard coat layer, adhesion under high temperature and high humidity (wet heat adhesive property) excellent.

It will be described in detail the laminated film of the present invention.

The laminated film of the present invention has a structure of as described above, the resin layer preferably contains particles (AB) with the acrylic resin (B) on the surface of the metal oxide particles (A) . The metal oxide particles (A) is preferably titanium oxide particles (A 1 ') and / or zirconium oxide particles (A 2'). Further, it is preferable that the resin layer comprises a polyester resin (D) having a fluorene structure, the polyester resin (D) is, either having no dicarboxylic acid component (Da 3) having a sulfonate group, polyester resin ( it is preferred to have less than 0.1 mol% relative to the amount of the dicarboxylic acid component (Da) constituting the D). Then, the thickness of the resin layer is preferably 10 ~ 50 nm.

To obtain a laminated film of the present invention, in the resin layer, and at least metal oxide particles (A), an acrylic resin (B), components derived from the oxazoline compound (C 1) and / or melamine it is necessary to contain a component (C 2) derived from the compound.

Acrylic resin having a monomer unit represented by formula (1) (b 1), the monomer units (b 2) represented by the formula (2), a monomer unit represented by the formula (3) (b 3) (B), and by containing the component derived from the oxazoline compound (C 1) and / or components derived from melamine compound (C 2), in the process of forming the resin layer, the metal oxide particles ( it is possible allowed to suppress aggregation of a). As a result, improving the transparency of the laminated film (reduce the haze) that, possible to suppress interference spots at the time of laminating a high refractive index hard coat layer, improving the adhesion between the high refractive index hard coat layer it becomes possible to improve the adhesion under high temperature and high humidity (wet heat adhesive property).

Furthermore, the aggregation of the metal oxide particles (A) can be suppressed, thereby enabling interference spots suppression in the case of stacking a high refractive index hard coat layer. This is because when the aggregation of the metal oxide particles (A) can be suppressed, it is possible to metal oxide particles (A) is present uniformly in the resin layer. Thus, it is possible to form a resin layer of uniform thickness, it is possible to increase the reflectance of the resin layer uniformly. As a result, a polyester film as a base material, a resin layer, the refractive index difference between the high refractive index hard coat is almost the same, interference spots is considered to be suppressed.

Further, if possible suppress aggregation of the metal oxide particles (A), since the adhesive property is low metal oxide particles of the hard coat layer (A) is present uniformly in the resin layer, adhesion between the hard coat layer it is possible to improve.
Acrylic Resin (B)]
Acrylic resin (B) contained in the resin layer of the present invention, the monomer unit (b 1) of the formula (1), a monomer unit represented by formula (2) (b 2), the formula ( it is important that a resin having a monomer unit (b 3) represented by 3).

Figure JPOXMLDOC01-appb-C000019

(In formula (1), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.).

Figure JPOXMLDOC01-appb-C000020

(Formula (In 2), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.).

Figure JPOXMLDOC01-appb-C000021

In (formula (3), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
Here, the acrylic resin (B) in the present invention, it is important that the resin having the formula (1) monomer unit represented by (b 1).

In the formula (1), when n is an acrylic resin having a monomer unit of less than 9, (for details of the water-based solvent, which will be described later.) Aqueous solvent unstable dispersibility of the metal oxide particles (A) in the to become. As described later, in the present invention, metal oxide particles, acryl resin, an oxazoline compound and / or melamine-based compound, and an aqueous solvent comprising a resin composition was coated on a polyester film as the base material by drying, it is preferable that the resin layer is formed. Therefore, the use of acrylic resin n in the formula (1) has monomer units of less than 9, the metal oxide particles (A) is or agglomeration or sedimentation in the resin composition, the metal oxide particles in the drying step (A ) may or aggregation. As a result, and if it becomes impossible to obtain a good laminate film transparency, in some cases interference spots during high refractive index hard coat layer laminated becomes poor. On the other hand, an acrylic resin having a monomer unit n in the formula (1) exceeds 34, since the extremely low solubility in aqueous solvents, coagulation of the acrylic resin is liable to occur in an aqueous solvent. Such aggregates are larger than the wavelength of visible light, in some cases interference spots or if during the high refractive index hard coat layer laminated be impossible to obtain a good laminate film transparency becomes poor. Further, it aggregates for inhibiting a uniform formation of the resin layer, which may adhesion between the hard coat layer is lowered.

Acrylic resin (B) in the present invention, in order to have the formula (1) monomer unit represented by (b 1) is expressed by the following equation (4) (meth) acrylate monomer (b 1 ') used as the starting material, it is necessary to polymerize.

The (meth) acrylate monomer (b 1 '), n in the formula (4) is represented by 9 or 34 an integer (meth) acrylate monomer, more preferably of 11 to 32 (meth) acrylate monomer, more preferably of 13 to 30 (meth) acrylate monomer.

Figure JPOXMLDOC01-appb-C000022

(In formula (4), R 1 group represents a hydrogen atom or a methyl group.)
(Meth) acrylate monomer (b 1 ') is, n is 9 or more 34 or less in the formula (4) (meth) is not particularly limited as long as acrylate monomer, specifically decyl (meth) acrylate, dodecyl ( meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, 1-methyl-tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, tetracosyl (meth) acrylate, triacontyl (meth) acrylate and the like, particularly dodecyl (meth) acrylate, tridecyl (meth) acrylate. These may be used alone, it is also possible to use mixtures of two or more thereof.

Further, the acrylic resin (B) in the present invention, it is important that the resin having the formula (2) represented by the monomer units (b 2).

In the formula (2), the use of an acrylic resin having a monomer unit containing only one hydrocarbon ring saturated, functions as a steric hindrance is insufficient, the metal oxide particles in the resin composition (A) aggregation or or precipitated metal oxide particles in the drying step (A) may be or agglomerate.

Such aggregates are larger than the wavelength of visible light, in some cases interference spots or if during the high refractive index hard coat layer laminated be impossible to obtain a good laminate film transparency becomes poor. Further, it aggregates for inhibiting a uniform formation of the resin layer, which may adhesion between the hard coat layer is lowered.

Acrylic resin (B) in the present invention is of the formula in order to have a monomer unit (b 2) represented by the formula (2) is expressed by the following equation (5) (meth) acrylate monomer (b 2 ') used as the starting material, it is necessary to polymerize.

Formula (5) as the (meth) acrylate monomer (b 2 '), bridged fused cyclic (with two or more rings share two atoms, respectively, having a structure bonded) (share one carbon atom has two cyclic structures are bonded structure) spirocyclic various cyclic structures such as, in particular, can be exemplified bicyclo, tricyclo, compounds having such tetracyclic group from the viewpoint of compatibility with the particular binder among them, containing a bicyclo group (meth) acrylate.

Figure JPOXMLDOC01-appb-C000023

(Formula (in 5), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)
The (meth) acrylate containing the bicyclo group, isobornyl (meth) acrylate, bornyl (meth) acrylate, di B & W dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate and the like, especially isobornyl (meth) acrylate.

Further, the acrylic resin (B) in the present invention, it is important that the resin having a monomer unit represented by the formula (3) (b 3).

R 5 groups in formula (3) is a hydroxyl group, a carboxyl group, a tertiary amino group, quaternary ammonium group, sulfonic acid group, a phosphoric acid group, the use of an acrylic resin having both no monomer units, acrylic resin the insufficient compatibility with an aqueous solvent, in the resin composition, or deposition acrylic resin, or aggregated or precipitated metal oxide particles (a) are with it, the metal in the drying step the oxide particles ( there is that a) is or aggregation.

Such aggregates are larger than the wavelength of visible light, in some cases interference spots or if during the high refractive index hard coat layer laminated be impossible to obtain a good laminate film transparency becomes poor. Further, it aggregates for inhibiting a uniform formation of the resin layer, which may adhesion between the hard coat layer is lowered.

Acrylic resin (B) in the present invention, in order to have a monomer unit represented by the following formula (6) (b 3) is represented by the formula (12) (meth) acrylate monomer (b 3 ') used as the starting material, it is necessary to polymerize.

The following compounds are exemplified as represented by the formula (12) (meth) acrylate monomer (b 3 ').

Figure JPOXMLDOC01-appb-C000024

In (Equation (6), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
The (meth) acrylate monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxy-butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene monoesters of a polyhydric alcohol and (meth) acrylic acid, such as glycol mono (meth) acrylate or, compounds by ring-opening polymerization of ε- Kapuroraputon to the monoester product and the like, in particular 2-hydroxyethyl ( meth) acrylate, 2-hydroxypropyl (meth) acrylate.

The (meth) acrylate monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, alpha such as maleic acid, beta-unsaturated carboxylic acid or a hydroxyalkyl (meth) acrylate and an acid anhydride such as a half ester and the like, especially acrylic acid and methacrylic acid are preferred.

The tertiary amino group-containing monomer, N, N- dimethylaminoethyl (meth) acrylate, N, N- diethylaminoethyl (meth) acrylate, N, N- dimethylaminopropyl (meth) acrylate, N, such as, N- dialkylaminoalkyl (meth) acrylate, N, N- dimethylaminoethyl (meth) acrylamide, N, N- diethylaminoethyl (meth) acrylamide, N, N- dimethylaminopropyl (meth) N, such as acrylamide, N- dialkylamino alkyl (meth) acrylamide and the like, in particular N, N-dimethylaminoethyl (meth) acrylate.

The quaternary ammonium base-containing monomer, an epihalohydrin in the tertiary amino group-containing monomer, benzyl halide, those allowed to act quaternizing agent such as alkyl halide preferably, specifically, 2- (methacryloyloxy ) ethyl trimethyl ammonium chloride, 2- (methacryloyloxy) ethyl trimethyl ammonium bromide, 2- (methacryloyloxy) ethyl trimethyl ammonium dimethyl phosphate such as (meth) acryloyloxy alkyl trialkyl ammonium salt, methacryloyl aminopropyl trimethylammonium chloride, methacryloyl (meth) acryloyl aminoalkyl trialkylammonium salt such as aminopropyl trimethylammonium bromide, tetrabutylammonium Tetra (meth) acrylates such as bromide (meth) acrylate, and tri-alkyl benzyl ammonium (meth 9 acrylates such as trimethylbenzylammonium (meth) acrylate. In particular 2- (methacryloyloxy) ethyl trimethyl ammonium chloride are preferred.

The sulfonic acid group-containing monomer, butylacrylamide sulfonic acid, 2-acrylamido-2-methylpropane (meth) acrylamide, such as acid - alkanesulfonic acid or, 2-sulfoethyl (meth) sulfonium acrylates such as (meth) acrylate, and the like, especially 2-sulfoethyl (meth) acrylate.

Examples of the phosphoric acid group-containing acrylic monomer, such as acidphosphoxyethyl ethyl (meth) acrylate. In particular acidphosphoxyethyl ethyl (meth) acrylate.

When manufacturing the laminate film of the present invention, the polyester film before crystal orientation is completed, the resin composition comprising an aqueous solvent is applied, stretching, how to complete the crystal orientation by a heat treatment are preferably used . Are possible heat treatment at a high temperature, it improves the adhesion between the substrate and the resin layer and, because more can be uniform in providing the resin layer of the thin film. In the case of forming a resin layer by this method, the acrylic resin (B) is dissolved in an aqueous solvent, emulsion, or as an aqueous capable of suspending is preferable in view of environmental pollution and explosion proof. Such, dissolved in water, an acrylic resin capable of emulsifying or suspending a monomer having a hydrophilic group copolymerizable or reactive emulsifier (an acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and salts thereof, etc.) or emulsion polymerization using a surfactant, suspension polymerization, can be produced by a method such as soap-free polymerization.

There is no particular limitation on the polymerization initiator is a general radical polymerization initiator such as potassium persulfate, ammonium persulfate, water-soluble peroxides such as hydrogen peroxide, or benzoyl peroxide and t- butyl hydroperoxide oil-soluble peroxides such as oxide, or azo compounds such as azodiisobutyronitrile, can be used.

Resin layer of a laminated film in the present invention, in addition to the component derived from at least the acrylic resin (B) and the component derived from the oxazoline compound (C 1) and / or the melamine compound (C 2), metal oxides containing particles (a), and the number average particle diameter of the metal oxide particles (a) are, it is important that the 50nm particles below or 3 nm.
[Metal oxide particles (A)]
By using such metal oxide particles (A), it is possible to increase the refractive index of the resin layer. As a result, the suppression of interference spots during the hard coat layer laminated, further since the number average particle diameter of the metal oxide particles (A) is sufficiently smaller than the wavelength of visible light, it is possible to enhance the transparency of the laminated film Become.

The metal oxide particles (A) in the present invention, malleability, rich in ductility, a good conductor of electricity and heat, the element having a metallic luster, that is, in the periodic table, boron (B), silicon (Si), arsenic ( the as), it refers to a tellurium (Te) and astatine (oxide particles of an element located to the left of diagonal line connecting At). Further, it is preferred over the alkaline earth metals (Group 2) at the periodic table is an oxide fine particles of elements located on the right.

Examples of such metal oxide fine particles, from the viewpoint of the suppression of interference spots, metal oxide particles having a high refractive index, preferably is suitable as a metal oxide particles of the above refractive index of 1.6. As the high refractive index metal oxide particles, TiO 2, ZrO 2, ZnO , CeO 2, SnO 2, Sb 2 O 5, indium-doped tin oxide (ITO), phosphorus-doped tin oxide (PTO), Y 2 O 5 , la 2 O 3, Al 2 O 3, and the like.

These metal oxide particles may be used singly or may be used in combination of two or more. From the viewpoint of dispersion stability and refractive index, titanium oxide particles (TiO 2) (A 1 ' ) and / or zirconium oxide particles (ZrO 2) (A 2' ) it is particularly preferred.

Here will be described a number average particle diameter of the metal oxide particles (A). Here, the number average particle diameter means a particle diameter determined by transmission electron microscopy (TEM). Magnification is 500,000 times, the outer diameter of 10 particles present in the screen, a number average particle size measured total 100 particles for 10 fields. Here, the outer diameter (a diameter of words particles, showing the longest diameter of the particles) the largest diameter of the particles represents, similarly in the case of particles having a cavity therein, the maximum size of the particles represent.

When the number average particle diameter of the metal oxide particles (A) is smaller than 3 nm, tends to aggregate because van der Waals force between the metal oxide particles is very large, a result of light scattered, transparency sometimes undesirable since decreases. On the other hand, if the number-average particle diameter of the metal oxide particles (A) is larger than 50 nm, from the viewpoint of transparency, preferably for or haze and the starting point light is scattered is increased, the reflectance is lowered Absent. The metal oxide particles (A) has a number average particle diameter of 3nm or more 50nm or less. Preferably 10nm or 45nm or less, more preferably 15nm or more 40nm or less.

The metal oxide particles (A), it is particles (AB) having an acrylic resin (B) to a part or the whole of its surface, more preferably (the resin layer containing particles (AB) is It will contain the metal oxide particles (a) and acrylic resin (B) of course). Resin layer, by containing such particles (AB), at the time of forming the resin layer using a later-described resin composition, suppress aggregation of the metal oxide particles in the drying process (A) and particles (AB) and, because it becomes possible to further improve transparency.

In the present invention, the metal oxide particles (A) is, the having an acrylic resin (B) on the surface, and the metal oxide particles (A) part or all of the surface acrylic resin (B ) it is, refers to adsorbed or adhere.

Although not particularly limited production method of particles (AB), the metal oxide particles (A) can be exemplified a method of surface treatment with an acrylic resin (B), specifically, the following ( i) the method of ~ (iv) are exemplified. In the present invention, the surface treatment means a treatment to adsorb or adhere the acrylic resin (B) all or part of the surface of the metal oxide particles (A).

(I) After the metal oxide particles (A) a mixture obtained by previously mixing the acrylic resin (B) was added to a solvent, a method of dispersing.

(Ii) in a solvent, a method of dispersing the additive metal oxide particles (A) and the acrylic resin (B) in this order.

(Iii) method in a solvent, the metal oxide particles (A) and the acrylic resin (B) is predispersed, mixing the resulting dispersion.

(Iv) a method in a solvent, followed by dispersing the metal oxide particles (A), to the obtained dispersion, the addition of the acrylic resin (B).

It is possible to attain the aimed effects by any of these methods.

Further, as an apparatus for performing dispersion, a dissolver, a high-speed mixer, a homomixer, Mida, a ball mill, a roll mill, a sand mill, a paint shaker, SC mill, annular type mills, pin-type mill or the like can be used.

As the dispersion method, using the apparatus to rotate the rotary shaft at a peripheral speed 5 ~ 15m / s. Rotation time is 5 to 10 hours.

Further, at the time of dispersion, it is more preferable in terms of enhancing the dispersibility of using dispersion beads such as glass beads. Bead diameter is preferably 0.05 ~ 0.5 mm, more preferably 0.08 ~ 0.5 mm, particularly preferably 0.08 ~ 0.2 mm.

Mixing, a method of stirring may be performed or carried out by shaking the container by hand, or using a magnetic stirrer or a stirring blade, ultrasonic irradiation, vibration dispersing the like.

Incidentally, to all or part of the surface of the metal oxide particles (A), the presence or absence of adsorption and adhesion of the acrylic resin (B) can be confirmed by the following analytical methods. Measuring object (e.g., metal oxide particles a resin composition comprising (A)), and Hitachi tabletop ultracentrifuge (Hitachi Koki Co., Ltd.: CS150NX) was centrifuged by (rpm 3,0000Rpm, separation time 30 minutes), after precipitated metal oxide particles (a) (and metal oxide particles (a) surface adsorption acrylic resin (B)), the supernatant was removed, concentrated to dryness sediment . Concentrated to dryness was sediment was analyzed by X-ray photoelectron spectroscopy (XPS), to confirm the presence or absence of the acrylic resin (B) in the surface of the metal oxide particles (A). The surface of the metal oxide particles (A), in the case where the total 100 mass% of the metal oxide particles (A), it was confirmed that the acrylic resin (B) is present more than 1 wt%, the metal oxide particles the surface of (a), the acrylic resin (B) is assumed to be absorbed and deposited.

Further, in the resin layer of the laminated film, the presence or absence of inclusion of particles (AB), by using the XPS while etching with an etching rate of 1 nm / min with argon ions from the resin layer side of the laminated film (SiO 2 basis) it can be confirmed. That is, if the presence of the acrylic resin (B) on the surface of the metal oxide particles (A) was confirmed, the metal oxide particles (A) is found to be particles (AB).

The content of the metal oxide particles (A) in the resin layer, on the entire resin layer is preferably not more than 20 wt% to 70 wt%. More preferably, 65 mass% or more and 25 mass% or less, more preferably not more than 30 mass% to 60 mass%. The content of the metal oxide particles (A), relative to the whole resin layer, by a more than 20 wt% 70 wt% or less, without damaging the film-forming property of the resin layer, the refractive index of the resin layer it can be improved. As a result, it becomes possible to sufficiently exhibit the desired clarity, interference unevenness suppression during the hard coat layer laminated.

Further, an acrylic resin having a monomer unit represented by formula (1) (b 1) and Formula monomer unit represented by (2) (b 2) a monomer unit represented by formula (3) (b 3) the content of (B), relative to the entire resin layer is preferably not more than 20 mass% to 5 mass%. More preferably, 7 wt% to 18 wt% or less, still more preferably 16 wt% or less 9 mass% or more. Within the above range, it is possible to suppress aggregation of the metal oxide particles (A) with each other, as a result, the refractive index of the resin layer, improving transparency, further, interference spots when the hard coat layer laminated It preferred because it becomes possible to sufficiently exhibit the suppression.
[Polyester resin having a fluorene structure (D)]
Resin layer in the present invention, containing the metal oxide particles (A), an acrylic resin (B), components derived from oxazoline compounds derived from components (C 1) and / or the melamine compound (C 2) and further preferably contains a polyester resin having a fluorene structure (D), more preferably, no polyester resin having a fluorene structure (D) is a dicarboxylic acid component having a sulfonic acid base (Da 3) or, relative to the amount of the dicarboxylic acid component constituting the polyester resin (D) (Da), preferably it has less than 0.1 mol%.

By using a polyester resin (D) having such a fluorene structure, the higher the refractive index of the resin layer is also improved adhesion between the hard coat layer. As a result, the high refractive index hard coat layer suppression or interference spots when stacked, adhesion between the high refractive index hard coat layer, it is possible to further improve the adhesion (wet heat adhesive property) under high temperature and high humidity more preferred because it becomes.

The polyester resin having a fluorene structure used in the present invention (D), refers to a polyester resin having an ester bond in the main chain or side chain, it can be obtained by the following methods I) or II). Also, I) and II) how to use the (dicarboxylic acid component (Da), glycol component (Db), and then component (Dc) as a constituent component, these method in which polycondensation reaction) may also be used.

How the I) the dicarboxylic acid component (Da), a glycol component (Db) and the components, allowed to polycondensation reaction both,
And II) one or more alcoholic groups (hydroxy groups), and component (Dc) a component having one or more carboxyl groups, method in which polycondensation reaction.

In the method of the above I), the dicarboxylic acid component (Da) is a dicarboxylic acid component having a fluorene structure (Da 1), a distinction is made between a dicarboxylic acid component having no fluorene structure (Da 2). Further, the glycol component (Db) is a glycol component having a fluorene structure (Db 1), is distinguished in having no glycol component a fluorene structure (Db 2). In the present invention, in order to introduce a fluorene structure in the polyester resin, it is preferable that the dicarboxylic acid component having a fluorene structure (Da 1) and / or glycol component having a fluorene structure (Db 1) are copolymerized.

Further, in the method of the above II), component (Dc), the components having a fluorene structure (Dc 1), a distinction is made between the component does not have a fluorene structure (Dc 2). In the present invention, in order to introduce a fluorene structure in the polyester resin (D), it is preferred that the component having a fluorene structure (Dc 1) are copolymerized.

Hereinafter, a polyester resin having a fluorene structure (D) as (hereinafter also referred to as "fluorene copolymerized polyester resin (D)".), But will be described in detail the case of using the method of I), II) of it is the same as the method also I) for instructions.

First, in the present invention, the dicarboxylic acid component (Da), contained the dicarboxylic acid alkyl ester of allowed ester forming derivatives. Further, the dicarboxylic acid component (Da), not only the dicarboxylic acid in the narrow sense, also includes tri- or higher carboxylic acid. Further, the dicarboxylic acid component (Da), also include an acid anhydride.

In the present invention, the glycol component (Da), not the narrow sense glycol alone, also includes trivalent or more polyols.

The dicarboxylic acid component having a fluorene structure (Da 1), for example, 9,9-bis (t-butoxycarbonyl methyl) fluorene, 9,9-bis [2-(t-butoxycarbonyl) ethyl] fluorene, 9, 9- bis [1-(t-butoxycarbonyl) ethyl] fluorene, 9,9-bis [2-(t-butoxycarbonyl) -1-methylpropyl] fluorene, 9,9-bis [2-(t-butoxy carbonyl) butyl] fluorene, 9,9-bis [5-(t-butoxycarbonyl) pentyl] Although fluorene and the like, but is not limited thereto.

Examples of the dicarboxylic acid component not having a fluorene structure (Da 2), an aromatic having no fluorene structure, aliphatic, dicarboxylic acids and trivalent or higher-valent carboxylic acid alicyclic be used. In the present invention, as such a dicarboxylic acid component (Da 2), terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimethyl terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 - it can be used bis phenoxyethane -p, p'-dicarboxylic acid, and the like. Further, As the aliphatic and dicarboxylic acids alicyclic, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1, and 4-cyclohexane dicarboxylic acid, and can be used ester-forming derivatives thereof.

Glycol component having a fluorene structure (Db 1) The 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dibenzyl phenyl] fluorene , 9,9-bis [4- (3-hydroxypropoxy) phenyl] fluorene 9,9-bis [4- (4-hydroxy-butoxy) phenyl] but fluorene and the like, but is not limited thereto.

Ethylene glycol as no glycol component a fluorene structure (Db 2), diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,7-heptane diol, 1,10-decanediol, neopentyl glycol, 4,4'-dihydroxy biphenol, o-, m-, and p- dihydroxybenzene, 4,4'-isopropylidene phenol, do not cyclopentane-1,2-diol, cyclohexane-1,2-diol, it can be used cyclohexane-1,4-diol is not limited thereto.

Copolymerization amount of the dicarboxylic acid component having a fluorene structure in the fluorene copolymerized polyester resin (D) (Da 1) is 40 mol relative to the amount of the dicarboxylic acid component constituting the fluorene copolymerized polyester resin (D) (Da) preferably at least% of, more preferably 80 mol% or more. The upper limit is not particularly limited, it is preferably not more than 95 mol%.

Moreover, the copolymerization amount of glycol component having a fluorene structure in the fluorene copolymerized polyester resin (D) (Db 1) is 40 mol relative to the amount of glycol component constituting the fluorene copolymerized polyester resin (D) (Db) preferably at least% of, more preferably 80 mol% or more. The upper limit is not particularly limited, particularly preferably not more than 95 mol%.

If the copolymerization amount of the dicarboxylic acid component having a fluorene structure (Da 1) or a glycol component (Db 1) is less than 40 mol%, the possibility of increasing index of refraction of the fluorene copolymerized polyester resin (D) is insufficient there is. The upper limit is not particularly limited, becomes high glass transition temperature of greater than 95 mole% copolymerization ratio when fluorene copolymerized polyester resin (D) is a resin layer using an in-line coating method described later stretching following capability becomes poor in case of providing a uniform resin layer may not be provided.

Moreover, the copolymerization amount of the dicarboxylic acid component having a fluorene structure in the fluorene copolymerized polyester resin (D) (Da 1) and glycol component (Db 1) having a fluorene structure constitutes the fluorene copolymerized polyester resin (D) when the total of the substance amount of substance quantity and a glycol component of the dicarboxylic acid component (Da) (Db) is 100 mol%, preferably at least 20 mol%, more preferably 40 mol% or more. The upper limit is not particularly limited, preferably 50 mol% or less.

In the present invention, the fluorene copolymerized polyester resin (D) is preferably water-soluble. The fluorene copolymerized polyester resin (D) to the water-soluble, can be introduced and a compound containing a carboxylic acid salt such as the side chain of the polyester resin (D), a hydrophilic component, such as a compound containing sulfonate groups preferable. The introduction of such a hydrophilic component, a dicarboxylic acid component (Da), a dicarboxylic acid component having a sulfonic acid salt (Da 3) and, by using a trivalent or higher-valent carboxylic acid component (Da 4), to achieve can.

The dicarboxylic acid component having a sulfonic acid salt (Da 3), for example, sulfoisophthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfo-naphthalene-2,7-dicarboxylic 5 [4-sulfophenoxy] isophthalic acid alkali metal salts, alkaline earth metal salts.

As the trivalent or higher-valent carboxylic acid component (Da 4), other polycarboxylic acids such as trimellitic acid, can also be used an acid anhydride. Specifically, trimellitic acid, 1,2,4,5-butane tetracarboxylic dianhydride (pyromellitic anhydride), 1,2,3,4-pentane tetracarboxylic dianhydride, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro furfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, ethylene glycol bistrimellitate dianhydride, 2,2 ', 3,3'-diphenyl tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, and the like.

However, in recent applications which wet heat adhesive property requirements as represented by display applications, when using a sulfonic acid base as the hydrophilic component of the polyester resin (D), hydrophilic strength of sulfonate Accordingly, there is the adhesive property between the hard coat layer at high temperature and high humidity conditions of the adherend decreases.

Therefore, in the present invention, the fluorene copolymerized polyester resin (D) is, either having no dicarboxylic acid component (Da 3) having a sulfonate group, a dicarboxylic acid component constituting the fluorene copolymerized polyester resin (D) (Da) it is preferred to have less than 0.1 mol% relative to the amount of. The amount of the dicarboxylic acid component having a sulfonic acid salt (Da 3) is more preferably at most 0.05 mol%, particularly preferably to have no (it is 0 mol%).

Therefore, in the present invention, the case of imparting hydrophilicity to the fluorene copolymerized polyester resin (D) to (water-soluble), it is preferable to copolymerize a trivalent or higher-valent carboxylic acid component (Da 4). By copolymerizing a trivalent or higher-valent carboxylic acid component (Da 4), it can be introduced carboxyl group into the side chain of the polyester resin (D). Further, the carboxyl group and ammonia, by neutralization with sodium hydroxide or the like, may be carboxylate groups. With carboxylate, it is possible to further increase the hydrophilicity.

In the present invention, as trivalent or higher-valent carboxylic acid component (Da 4), it is more preferable to use a tetracarboxylic acid. Tetracarboxylic acids, as compared to trivalent carboxylic acid such as trimellitic acid, because it has many carboxyl groups necessary to impart hydrophilicity to the fluorene copolymerized polyester resin (D), fluorene copolymerized polyester resin it is possible to reduce the proportion of the polyvalent carboxylic acid component (Da 4) in (D) a dicarboxylic acid component in (Da). Thereby, it is possible to improve the adhesion between can be increased sufficiently the number average molecular weight at the time of polymerization of the polyester resin, a high refractive index hard coat layer to be laminated like.

Incidentally, the copolymerization of polycarboxylic acid component, the polyester polyol obtained by reacting a dicarboxylic acid component (Da) and the glycol component (Db) (polyester oligomer), trivalent or higher-valent carboxylic anhydride (Da 4 ) it is preferable to use a method of introducing a carboxyl group into the side chain of the polyester resin (D) by reacting the. By using such a method, it is possible to introduce a carboxyl group into the side chain of the polyester resin (D) more efficiently.

Polycarboxylic acid anhydrides used in this case the amount of substance of (Da 4) (Da 4 m ( mol)) is the amount of substance of the glycol component used in the esterification reaction (Da) and (Dam, (mol)), a dicarboxylic it is preferable that the amount of substance of the acid component (Dbm (mole)) difference (Dam-Dbm (mole)) of 0.5-1.0 times the substance amount of. With such a preferable range, excellent adhesive property at high temperature and high humidity conditions to a substrate of the prepared the resin layer, while the number-average molecular weight of the polyester increases sufficiently.

Next, an example of a manufacturing method of the fluorene copolymerized polyester resin (D). First, the dicarboxylic acid component having no fluorene structure succinic acid or its ester-forming derivative as the (Da 2), 9,9-bis [4- (2-hydroxyethoxy) as a glycol component having a fluorene structure (Da 1) phenyl] fluorene, perform an esterification reaction using a glycol component and a catalyst such as ethylene glycol as no glycol component a fluorene structure (Db 2), to obtain a polyester polyol. At this time, 9,9-bis amount of [4- (2-hydroxyethoxy) phenyl] fluorene and ethylene glycol is preferably 1.01 to 2.0 times mole based on the total dicarboxylic acid component. Within the above preferred range, it is possible to smoothly polymerized polyester polyol in the presence of an excess of glycol component, while the number-average molecular weight distribution of the polyester resin is increased sufficiently.

Also, tetraisopropyl titanate as a catalyst, tetra -n- butyl titanate or titanium-based, antimony trioxide and antimony-based catalyst of germanium such as germanium oxide, zinc acetate, manganese acetate, catalyst such as dibutyltin oxide the like, preferably tetra -n- butyl titanate is used. The esterification reaction in this case there is no particular restriction on the temperature and time, may be carried out in a known range.

Although an addition of the next resultant polycarboxylic acid anhydride to the polyester polyol (Da 4), if such a reaction is performed for about 1 to 10 hours at 160 ~ 200 ° C., the polyester polyol of interest are obtained. The said catalyst may be added the same extent when.

In the present invention, the intrinsic viscosity of the fluorene copolymerized polyester resin (D) is not particularly limited, in order to make adhesion to the adherend such as a hard coat layer made favorable, it is 0.3 dl / g or more It is preferred. The upper limit is not particularly limited intrinsic viscosity, it is preferably not more than 0.8 dl / g in terms of handling properties. Fluorene copolymerized polyester resin having an intrinsic viscosity of interest (D) is obtained by adjusting the melt polymerization conditions such as polymerization time and polymerization temperature.

The glass transition point of the fluorene copolymerized polyester resin (D) (hereinafter, sometimes abbreviated as Tg) is preferably 50 ~ 170 ° C., more preferably 50 ~ 0.99 ° C.. Within the above preferred range, excellent wet heat adhesive property while it uniformly Coating resin layer in an in-line coating method described later. To the above range is the tg, as fluorene copolymerized polyester resin (D) a dicarboxylic acid component other than the dicarboxylic acid component having a fluorene structure (Da 2), there are methods such as using an aliphatic dicarboxylic acid component.

The acid value of the fluorene copolymerized polyester resin (D) is preferably at 20 mgKOH / g or more, more preferably 30 mgKOH / g or more. By the acid value within the above range, it is possible to improve the adhesiveness, particularly the wet heat adhesive property between the hard coat layer. The acid value to the above range, the polymerization time of the fluorene copolymerized polyester resin (D), is obtained by adjusting the amount of polycarboxylic acid anhydride to be reacted with the polyester polyol (Da 4).

In the present invention, it is preferable that the content of the fluorene copolymerized polyester resin in the resin layer (D) is not more than 30 wt% 5 wt% or more based on the whole the resin layer.

The content of the fluorene copolymerized polyester resin (D) is in the above range, a high refractive index of the resin layer is achieved, the substrate, the refractive index difference between the resin layer and the high refractive index hard coat layer It decreases, thereby reducing the interference spots. It is possible to further improve the adhesion between the high refractive index hard coat layer.
[Component derived from the oxazoline compound (C 1) and / or components derived from melamine compound (C 2)]
Resin layer of a laminated film in the present invention, at least the metal oxide particles (A), containing an acrylic resin (B), further from the component (C 1) and / or melamine compounds derived from oxazoline compound it is important to contain a component (C 2).

In addition to the acrylic resin (B), with an oxazoline-based compound (C 1 ') and / or the melamine compound (C 2' a), by allowed to form a resin layer, in the process of forming the resin layer, the metal it is possible allowed to suppress aggregation of the oxide particles (a), as a result, the transparency of the laminated film, it is possible to increase the reflectance, as a result, upon laminating the hard coating, transparency, adhesiveness , it is possible to obtain an excellent laminate film visibility.

Furthermore, the aggregation of the metal oxide particles (A) can be suppressed, thereby enabling interference spots suppression in the case of stacking a high refractive index hard coat layer. This is because when the aggregation of the metal oxide particles (A) can be suppressed, it is possible to metal oxide particles (A) is present uniformly in the resin layer. As a result, it forms the resin layer of uniform thickness, it is possible to increase the reflectance of the resin layer uniform is considered to contribute to the interference spots suppression.

Furthermore, the aggregation of the metal oxide particles (A) can be suppressed, since the adhesiveness is low metal oxide particles of the hard coat layer (A) is eliminated to be present locally, adhesion between the hard coat layer it is possible to improve.

The resin composition of the present invention, as described above, in an aqueous solvent, part or all of the surface in the aforementioned acrylic resin of the metal oxide particles (A) (B) is present in the adsorbent-adhering it is preferable. The resin composition comprising a water-based solvent, was coated on a polyester film as a base material, followed by drying the resin layer is formed. If the particle content is 70 mass% or less in the resin layer, the metal oxide particles (A) an acrylic resin which is adsorbed and adhered to the surface of the (B) has a steric hindrance, of the particles aggregation is considered relatively be suppressed. However, when the particle content exceeds 70 mass%, it becomes difficult to suppress the aggregation of the particles.

However, in the resin composition, when containing 'component (C 2 derived from and / or melamine-based compound) oxazoline compound (C 1)', even if the particle content exceeds 30 parts by weight, it is possible to suppress the aggregation of the particles.

The oxazoline compound (C 1 ') and / or the melamine compound (C 2' Although) details the mechanism that aggregation can be prevented and use is still unclear, and estimated current as follows.

The aqueous solvent, the surface of the metal oxide particles (A), there acrylic resin (B) is adsorbed, adhered, oxazoline compound (C 1 ') and / or the melamine compound (C 2') also water based It is uniformly present in a solvent. However, coated on a polyester film substrate, in the process of drying, the acrylic resin (B) and oxazoline compound (C 1 '), also acrylic resin (B) and melamine compound (C 2') are mutually because of the affinity, the outer metal oxide particles acrylic resin (B) is adsorbed or adhere (a), oxazoline compound (C 1 '), and / or the melamine compound (C 2') is wrapped, a drying while maintaining the state, is considered to form a resin layer. In this drying process, since the particles are wrapped in an oxazoline-based compound (C 1 '), and / or the melamine compound (C 2'), in the process of being concentrated in a drying, to keep the distance between particles longer possible and will, as a result particle agglomeration is assumed to be suppressed.

The component derived from the oxazoline compound in the present invention (C 1), described below oxazoline compound (C 1 ') as well, oxazoline compound (C 1') is or acrylic resin (B), (B ) other than the acrylic resin or a melamine-based compound (C 2 'case of forming) etc. and crosslinked structure, oxazoline compound (C 1' comprises components derived from) (e.g. residues, etc.).

Oxazoline compounds as the (C 1 '), but it if not particularly limited as it has at least one per molecule an oxazoline group or an oxazine group alone polymerizing an addition-polymerizable oxazoline-group-containing monomer, or other monomers polymerized polymer with are preferred.

Examples of the addition-polymerizable oxazoline-group containing monomers, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline , mention may be made of 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline. These may be used alone, it is also possible to use mixtures of two or more thereof. Among these, it is preferable 2-isopropenyl-2-oxazoline is easily be obtained industrially. Other monomers include, without limitation as long as the addition-polymerizable oxazoline-group-containing monomer and copolymerizable monomer, for example, the alkyl acrylates, alkyl methacrylates (the alkyl group, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, 2-ethylhexyl group, (meth) acrylic acid esters or acrylic acid such as cyclohexyl group), methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) unsaturated carboxylic acids such as acrylonitrile, unsaturated nitriles such as methacrylonitrile; acrylamide, methacrylamide, N- alkylacrylamide , N- alkylmethacrylamide N, as the N- dialkyl acrylamide, N, N- dialkyl methacrylate (the alkyl group, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, a 2-ethylhexyl group unsaturated amides such as cyclohexyl group), vinyl acetate, vinyl propionate, vinyl esters such as those obtained by adding acrylic acid, polyalkylene oxide to the ester portion of the methacrylic acid, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether s, ethylene, alpha-olefins such as propylene, vinyl chloride, vinylidene chloride, halogen-containing alpha, beta-unsaturated monomers such as vinyl fluoride, styrene, alpha-methyl styrene, alpha etc, beta-unsaturated aromatic can be mentioned a family monomers, these one or more kinds It may be used monomers.

The component derived from the melamine compound in the present invention (C 2), described below melamine compound (C 2 ') as well, the melamine compound (C 2') is or acrylic resin (B), (B ) other than the acrylic resin or an oxazoline-based compound (C 1 'case of forming) etc. and crosslinked structure, the melamine compound (C 2' containing a component derived from) (e.g. residues, etc.).

As the melamine-based compound (C 2 '), for example, melamine, melamine and formaldehyde methylolated melamine derivative obtained by condensing, by reacting a lower alcohol methylolated melamine partially or completely compound etherified, and it can be used a mixture thereof. Specifically, compounds having a triazine and methylol group is particularly preferred. The monomer as the melamine compound may be either the condensate consisting of dimer or more multimer, or a mixture thereof. Examples of the lower alcohol used for the etherification can be used methyl alcohol, ethyl alcohol, isopropyl alcohol, n- butanol, isobutanol. The group, an imino group, methylol group, or an alkoxymethyl group such as methoxymethyl group or butoxymethyl group those having in one molecule, an imino group type methylated melamine resin, methylol group type melamine resin, methylol group type methylated and the like melamine resin, complete alkyl type methylated melamine resin. And most preferably methylolated melamine resin among them. Furthermore, to promote the thermal curing of the melamine compound may be an acidic catalyst such as for example p- toluenesulfonic acid.

The use of such a melamine-based compound (C 2 '), as mentioned above, in the process of drying the resin composition, can inhibit the metal oxide particles (AB) to aggregate, the transparency of the resin layer, it is possible to increase the reflectivity, as a result, upon laminating the hard coating, transparency, adhesiveness, it is possible to obtain an excellent laminate film visibility.

In the present invention, components derived from the oxazoline compound (C 1) and / or components derived from melamine compound (C 2) is not impaired and the metal oxide particles (A), the effect of the acrylic resin (B) if it is possible to use any amount.

The amount of starting material is an oxazoline compound of the component derived from the oxazoline compound (C 1) (C 1 ' ), also raw melamine compound is a component (C 2) derived from the melamine compound (C 2') is preferably 10-50 quality portion of the total 100 parts by weight of the metal oxide particles (a) and the acrylic resin (B), more preferably 15 to 45 parts by weight. With 10 parts by mass or more, the resin layer, it is possible to express the effect of the component derived from the oxazoline compound (C 1) and / or components derived from melamine compound (C 2).

In addition to components derived from the component (C 1) and / or melamine compounds derived from oxazoline compound (C 2), other compounds, for example, carbodiimide compounds, epoxy compounds, aziridine compounds, amide epoxy compounds, titanium titanate coupling agents such as chelating, methylolated or alkylolated urea-based compound, or the like can be used in any acrylamide compound.
[Polyester film]
In the laminated film of the present invention, it describes a polyester film used as a substrate film. Polyester The first, a general term for a polymer having an ester bond in the main chain, ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, ethylene-.alpha., beta - bis (2-chlorophenoxy) it can be preferably used for at least one component selected from ethane-4,4'-dicarboxylate.

Polyester film using the polyester is preferably one which is biaxially oriented. The biaxially oriented polyester film, generally, is stretched, each 2.5 to 5 times the polyester sheet or film of unstretched state in the width direction perpendicular to the longitudinal direction and the longitudinal direction, then, is subjected to a heat treatment, crystals are those oriented is completed, it refers to showing a pattern of biaxial orientation in wide angle X-ray diffraction. When the polyester film is biaxially oriented, thermal stability, particularly stability and mechanical strength sufficient size, it is also flatness good.

Further, in the polyester film, various additives, e.g., antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic easy lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, may be added to the extent that such nucleating agent does not deteriorate the characteristics.

The thickness of the polyester film is not particularly limited, but is appropriately selected depending on the application and the kind, the mechanical strength, in view of handling property, usually preferably 10 ~ 500 [mu] m, more preferably 38 ~ 250 [mu] m , most preferably 75 ~ 150μm. Further, the polyester film may be a composite film by co-extrusion, the obtained film may be a combined film bonding by various methods.
[Resin composition of the resin layer and methods for their preparation]
The resin composition of the resin layer in the present invention contains at least the metal oxide particles (A) and the acrylic resin (B), oxazoline compound (C 1 ') and / or the melamine compound (C 2' a) and the number average particle diameter of the metal oxide particles is a composition comprising a resin is 3nm or more 50nm or less.

If necessary, (B) other than the acrylic resin, other compounds, for example, carbodiimide compounds, epoxy compounds, aziridine compounds, amide epoxy compounds, titanate coupling agent, such as titanium chelate, methylolated or alkylolated urea system compound, may contain acrylamide-based compound.

Further, various additives, for example, an organic easy lubricants, organic or inorganic fine particles, such as antistatic agents may be added to the extent that does not deteriorate its characteristics.

Resin composition using an aqueous solvent is carried out at least an aqueous dispersion or water-soluble acrylic resin (B), the metal oxide particles (A), the added once dispersed in the order of (A), (B), a metal on the surface of the oxide particles (a), after adsorbing the acrylic resin (B), was added oxazoline compound (C 1 ') and / or the melamine compound (C 2'), an aqueous solvent desired mass mixing ratio, it can be produced by stirring. Then, the polyester resin (D) and having a fluorene structure as necessary, various additives (easy lubricants, inorganic particles, organic particles, a surfactant, an antioxidant) to give the desired mass ratio in the resin composition in mixing, it can be produced by stirring.

The metal oxide particles (A) acrylic resin (B) in addition, as a method for performing dispersion, a paint shaker, SC mill, annular type mills generally circumferential speed using a pin-type mill or the like at 5 ~ 15 m / s rotate. Rotation time is 5 to 10 hours. During dispersion, it is preferred from the viewpoint of enhancing dispersibility of using dispersion beads such as glass beads. Bead diameter is preferably 0.05 ~ 0.5 mm, more preferably 0.08 ~ 0.5 mm, particularly preferably 0.08 ~ 0.2 mm.

Mixing, a method of stirring, or conducted by shaking the container by hand, or using a magnetic stirrer or a stirring blade can be ultrasonic irradiation, vibration dispersing the like performed.

An aqueous dispersion or water-soluble acrylic resin (B), acrylic resin, copolymerization of a monomer having a hydrophilic group and (acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and salts thereof, etc.), Ya reactive emulsifier emulsion polymerization using a surfactant, suspension polymerization, can be produced by a method such as soap-free polymerization.

There is no particular limitation on the polymerization initiator is a general radical polymerization initiator such as potassium persulfate, ammonium persulfate, water-soluble peroxides such as hydrogen peroxide, or benzoyl peroxide and t- butyl hydroperoxide oil-soluble peroxides such as oxide, or azo compounds such as azodiisobutyronitrile, can be used.
[Formation method and a manufacturing method of a multilayer film of the resin layer]
In the present invention, at least the metal oxide particles (A) and the acrylic resin (B), oxazoline compound (C 1 ') and / or the melamine compound (C 2') a resin composition containing on a polyester film coated, when the resin composition contains a solvent, by drying the solvent, it is possible to form the resin layer on the polyester film.

In the present invention, when allowed to contain a solvent in the resin composition, it is preferable to use a water-based solvent as the solvent. By using an aqueous solvent, it can suppress an abrupt evaporation of the solvent in the drying step, not only can form a uniform composition layer is because it is excellent in terms of environmental impact.

Here, the aqueous solvent, water or a mixture of water and methanol, ethanol, isopropyl alcohol, and butanol, ketones such as acetone and methyl ethyl ketone, ethylene glycol, diethylene glycol, soluble in water, such as glycols such as propylene glycol, the organic solvent is refers to those mixed in any ratio.

Coating method to a polyester film of the resin composition is important for an in-line coating method. The in-line coating method is a method of performing coating within the production of the polyester film process. Specifically, it refers to a method of performing coating at any stage before winding up heat treated after biaxial stretching after melt extrusion of a polyester resin, usually, substantially non obtained by after melt extrusion-quenching unstretched amorphous state (non-oriented) polyester film (a film), then longitudinally stretched uniaxially stretched (uniaxially oriented) polyester film (B film), or biaxially before the heat treatment is further stretched in the width direction stretching (biaxial orientation) is applied to one of the film of a polyester film (C film).

In the present invention, the A film before the crystal orientation is completed, B film, in any one of polyester film, a resin composition is applied, then stretching the polyester film in a uniaxial direction or biaxial direction, of the solvent it is preferable to employ a method of providing a resin layer with complete crystal orientation of the polyester film subjected to a heat treatment at a higher temperature than the boiling point. According to this method, a film of a polyester film, coating and drying of the resin composition (i.e., formation of the resin layer) is advantageous in production cost since it is possible to simultaneously. Further, it is easy to further reduce the thickness of the resin layer in order to perform the stretching after coating.

Among them, longitudinally uniaxially stretched film (B film), a resin composition is applied, then stretched in the width direction, it is superior method of heat treatment. After applying the unstretched film, compared with a method of biaxial stretching, since the stretching process is small one, defects and cracks of the composition layer is hardly generated by stretching, transparency and smoothness in good composition layer This is because that can be formed.

The resin layer in the present invention, the various advantages described above, it is important to be provided by the in-line coating method. Here, the coating method of the resin composition of the polyester film, known coating methods, for example, a bar coating method, reverse coating method, gravure coating method, die coating method, may be any method such as blade coating method.

Accordingly, the method of forming the best resin layer in the present invention, a resin composition using an aqueous solvent, was coated using an in-line coating method on a polyester film, drying is a method of forming by heat treatment. And more preferably, a method for in-line coating a resin composition B film after uniaxial stretching. The method of manufacturing a laminated film of the present invention, the drying in order to complete the removal of the solvent of the resin composition, can be carried out in a temperature range of 80 ~ 130 ° C.. The heat treatment in order to complete the formation of the resin layer to complete the thermosetting resin composition together to complete the crystal orientation of the polyester film, may be carried out in a temperature range of 160 ~ 240 ° C..

Further solid concentration of the resin composition is preferably 10 mass% or less. By solid concentration is 10 wt% or less, the resin composition can provide good coating properties, it is possible to produce a laminated film provided with a transparent and uniform composition layer.

Incidentally, the solid content concentration, relative to the weight of the resin composition, represents the mass ratio of the mass obtained by subtracting the mass of the solvent from the resin composition (i.e., in the solid concentration] = [(Resin composition mass) - (weight of solvent)] is / [mass of the resin composition).

Next, a method of manufacturing the laminated film of the present invention, polyethylene terephthalate as the polyester film (hereinafter, PET) the case of using the film is described as an example, but not limited thereto. First, after thoroughly vacuum-dried pellets of PET, and fed to an extruder, melt-extruded into a sheet at about 280 ° C., to produce a cooled and solidified allowed to unstretched (unoriented) PET film (A film). Obtaining a monoaxially oriented PET film (B film) The film 80 to 120 in a heated roll ℃ by stretching 2.5-5.0 times in the longitudinal direction. Applying a resin composition of the present invention prepared to a predetermined concentration on one side of this B film.

In this case, it may be subjected to surface treatment such as corona discharge treatment the coated surface of the PET film prior to coating. By performing a surface treatment such as corona discharge treatment, it is possible to improve the wettability of the PET film of the resin composition, to prevent cissing of the resin composition to form a resin layer having a uniform coating thickness. After coating, and held with clips the ends of the PET film leads to 80 ~ 130 ° C. heat treatment zone (preheating zone) to dry the solvent of the resin composition. After drying the width direction 1.1 to 5.0 times stretching. Subsequently subjected to heat treatment for 1 to 30 seconds leads to 160 ~ 240 ° C. heat treatment zone (thermal fixing zone), to complete the crystal orientation.

This heat treatment step (a thermal fixing process), the width direction or longitudinal direction may be performed from 3-15% relaxation treatment as required. The laminated film thus obtained becomes a laminated film excellent in transparency and anti-reflection properties.

The thickness of the resin layer in the present invention is preferably 10nm or more 50nm or less. More preferably at 10nm or more 45nm or less, more preferably 10nm or more 40nm or less. The thickness of the resin layer, by a 10nm or 50nm or less, it becomes possible to sufficiently exhibit the suppression of interference spots. Also by this film thickness is less than 15 nm, agglomeration of the metal oxide particles becomes possible inhibition was found that it is possible further improve the reflectance. This detailed mechanism is unknown, the thinning of the coating to reduce the probability of contact particles in the drying process, thereby suppressed particle agglomeration, the roughness of the coating surface is reduced. As a result, it estimates that diffused light coating film surface has been improved reflectivity by reduced.
[Evaluation method of measuring methods and effect of characteristics]
Evaluation method of measuring methods and effect of characteristics in the present invention are as follows.
(1) Measurement of total light transmittance, initial Haze Rating total light transmittance and the initial haze, normal (23 ° C., 50% relative humidity) in, after the laminated film sample was allowed to stand for 40 hours, Nippon Denshoku Kogyo (Co. ) manufactured by turbidimeter using "NDH5000", "total test methods light transmittance of the transparent plastic material" (1997 edition total measurement of light transmittance JIS K 7361-1), measurements of the initial haze JIS K 7136 It was carried out in a manner that conforms to the "how to determine the haze of the transparent material" (2000 edition). The resin layer of the sample was measured by irradiating light from the laminated side. Samples things one side of a square 50mm and 10 sample preparation, once each, and the average values ​​measured a total of 10 times and haze value of the sample.
(2) a film sheet was cut to the reflectance A4 cut size vertically and horizontally divided into three, with a total of 9 points as a measuring sample. The long side and the longitudinal direction. Measurement of the spectral reflectance measurement surface black gloss tape 50mm wide on the rear surface of (the resin layer) (Yamato Co., Ltd., vinyl - Rutepu Nanba200-50-21: black), and no nipped bubbles after the longitudinal direction of the sample and the tape were bonded combined as cut into sample pieces of about 4cm square spectrophotometer (manufactured by Shimadzu Corporation, UV2450) measuring the spectral reflectance at an incident angle of 5 ° to did. Direction to set the sample to the measuring instrument, the combined longitudinal sample in the direction of back and forth towards the front of the instrument. Note for scaling the reflectance, Al 2 O 3 was used plate that comes as standard reflection plate. Reflectivity was determined the reflectance of the resin layer side at a wavelength of 550 nm. Incidentally, the measured value was used an average value of 10 points.
(3) in the resin layer side of the adhesive laminate film with the laminate, the UV-curable resin mixed in the following proportions, the film thickness after curing with a bar coater was uniformly coated to a 2 [mu] m.
, Adjustment and titanium dioxide fine particles of the hard coat agent (manufactured by Ishihara Sangyo Kaisha, Ltd., TTO-55B): 30 parts by mass carboxylic acid group-containing monomer (Toa Gosei Co., Ltd., Aronix M-5300): 4.5 Weight part cyclohexanone: 65.5 parts by mass the above mixture was dispersed by a sand grinder mill, the average particle size of the dispersion was adjusted to 55nm of titanium dioxide fine particles.

The dispersion of the titanium dioxide fine particles, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) and photoinitiator (manufactured by Ciba-Geigy, Irgacure 184) the total amount of monomer (dipentaerythritol - Le total amount of hexaacrylate and an anionic monomer) to 5% by mass, mixed and the refractive index of the hard coat layer was adjusted to 1.65.

Then, condensing high-pressure mercury lamp having an irradiation intensity of 120 W / cm was set from a surface formed by laminating a UV curable resin layer to the height of 9cm (manufactured by Eye Graphics Co., Ltd., H03-L31), the integrated irradiation intensity irradiating ultraviolet radiation so that 300 mJ / cm 2, to cure the hard coat layer was obtained a hard coating laminated polyester film laminated on a polyester film. In addition, industrial UV checker to the cumulative radiation intensity measurement of ultraviolet (Japan Storage Battery Co., Ltd., UVR-N1) was used. The resulting hard coat laminated polyester film was, in the hard coat layer surfaces of the resulting hard coat laminated polyester film, put in 100 cross-cut of 1mm 2, "Scotch tape (registered trademark)" (Nichiban Co., Ltd., CT405AP ) paste, after pressing at a load of 1.5 kg / cm 2 using a hand roller, and rapidly peeled off in the direction of 90 degrees with respect to the hard coat laminated polyester film. The number of the adhesive remaining grating were 4 out. C level with practical problems, B is a practical level, and The good ones A and S.

S: 90 ~ 100 pieces remaining A: 80 ~ 89 pieces remaining B: 50 ~ 79 pieces remaining C: 0 ~ 50 fewer than the remaining.
(4) to the resin layer side of the wet heat adhesive laminated polyester film, (3) in the same manner as, by laminating a hard coat layer, to obtain a hard coat laminated polyester film. Further, the hard coat laminated polyester film obtained, the temperature 70 ° C., allowed to stand for 240 hours in 90% relative humidity constant temperature and humidity vessel to obtain a sample for wet-heat adhesion test. The obtained wet heat bonding test sample, (3) in the same manner as performed adhesion test was carried out four stages evaluated by the number of remaining lattice.

C level with practical problems, B is a practical level, and The good ones A and S.

S: 90 ~ 100 pieces remaining A: 80 ~ 89 pieces remaining B: 50 ~ 79 pieces remaining C: 0 ~ 50 fewer than the remaining.
The number average particle diameter (5) Number average particle size metal oxide particles (B) was determined by observing the cross-sectional structure of the laminated film by a transmission electron microscope (TEM). Magnification and 500,000 fold, the outer diameter of 10 particles present in the screen, a total of 100 particles for 10 fields was measured to determine the average particle size. If there is no 10 particles in the screen is to observe the different locations in the same conditions, by measuring the outside diameter of the particles present in the screen, measuring the outer diameter of 100 particles in total It was defined as the average value each. Here, the outer diameter (a diameter of words particles, showing the longest diameter of the particles) the largest diameter of the particles represents, similarly in the case of particles having a cavity therein, the maximum size of the particles represent.
(6) by observing the cross section using a thickness transmission electron microscope of the resin layer (TEM), to measure the thickness of the resin layer on the polyester film. The thickness of the resin layer, was read the thickness of the resin layer from the images taken with 200,000 times magnification by TEM. And an average value by measuring a resin layer thickness of 20 points in total.
(7) visibility (interference spots)
(3) and in the same manner, a hard coat layer having a thickness of 2 [mu] m (refractive index 1.65) was obtained hard coat laminated polyester film laminated on the laminated polyester film.

Then, from the resulting laminated film for optical, 8 cm cut the size of the sample (laminated polyester film width direction) × 10 cm (laminated polyester film longitudinal direction), black gloss tape (Yamato (strain opposite surface of the hard coat layer ) Co., Ltd., vinyl - Rutepu No.200-50-21: the black), was bonded so as not bitten bubbles.

The three-wavelength fluorescent lamp sample in a dark room (Panasonic Co., 3 band type daylight (F · L 15EX-N 15W)) placed immediately below 30cm, the observed degree of interference spots visually while changing the viewing angle and, the following evaluations were carried out. It was as good of not less than A.

S: A interference spots can not be seen almost: interference spots may look slightly B: weak interference spots can be seen.

C: strong interference spots.
(8) Composition Analysis of the composition analysis resin layer of the resin layer, for the surface of the laminated film, X-rays photoelectron spectrometer (ESCA), Fourier transform infrared spectrophotometer (FT-IR) ATR method, time-of-flight secondary It was carried out by ion mass spectrometer (TOF-SIMS). Further, the resin layer was dissolved by extraction with a solvent, after fractionated by chromatography, proton nuclear magnetic resonance spectroscopy (1H-NMR), carbon nuclear magnetic resonance spectroscopy (13 C-NMR), Fourier transform infrared spectrophotometer meter (FT-IR) by analyzing the structure and composition analysis of the pyrolysis gas chromatography mass spectrometry (GC-MS) was carried out resin layer.

By the above method, the metal oxide particles in the resin layer (A), particles (AB), acrylic resin (B), oxazoline compound (C 1 '), components derived from the oxazoline compound (C 1), melamine compound (C 2 '), to confirm the presence or absence of the component (C 2) derived from the melamine compound.

In the resin layer, when containing the compound A, the case of not containing was B.

Incidentally, the characteristics of the resulting laminated film in the following Examples and Comparative Examples are shown in Tables 1 to 4.
<Example 1>
First, the resin composition 1 was prepared as follows.

· Metal oxide particles (A):
Metal oxide particles in which zirconium oxide dispersion SZR-CW (manufactured by Sakai Chemical Industry Co., Ltd., zirconium oxide particles: number average particle diameter of 20 nm) was used.

Acrylic resin (B):
Stirrer, thermometer, a normal of the acrylic resin reaction vessel equipped with a reflux condenser, was charged with 100 parts of isopropyl alcohol as a solvent, was held in stirred and heated 100 ° C..

Among this, 'as, nonadecyl methacrylate 40 parts of n = 19, (meth) acrylate (b 2 (meth) acrylate (b 1)' as), isobornyl methacrylate 40 parts having two rings, other hydroxyl as the a (meth) acrylate (b 3 '), was added dropwise over the mixture for 3 hours consisting of 20 parts of 2-hydroxyethyl acrylate. After completion of dropwise addition, the mixture was heated for 1 hour at 100 ° C., it was charged then t- butyl consisting peroxy 2-ethyl hexa benzoate 1 part added catalyst mixture. Then it cooled after heating 3 hours at 100 ° C., to obtain an acrylic resin (B). The structural formula of the obtained acrylic resin (B) are shown below. (However, this structure is, b 1 in its chemical structure ', b 2', b 3 ' merely represents that it has a, not intended to define the order and number of each structural unit.)

Figure JPOXMLDOC01-appb-C000025

(In the formula, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation. Moreover, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or, ,., which represents a phosphate group)
- water-based solvent: pure water.

· Particles (AB) and a mixture of acrylic resin (B):
In an aqueous solvent, adding the metal oxide particles (A) and the acrylic resin (B) in this order, dispersed in the following manner, to obtain a mixture of particles (AB) and the acrylic resin (B). (Method of the (ii).) The addition amount ratio of the metal oxide particles (A) and the acrylic resin (B) (weight ratio) was (A) / (B) = 45/10 (Note mass ratio , was obtained by rounding off the first decimal place). Dispersion treatment was conducted by rotating carried out using a homomixer, at a peripheral speed of 10 m / s 5 hours. Further, in the finally obtained mixture, the mass ratio of the particles (AB) and acrylic resin (B), (AB) / (B) = 45/10 and which was (The mass ratio of the first decimal was obtained by rounding off position).

Incidentally, the obtained particles (AB), Hitachi tabletop ultracentrifuge (Hitachi Koki Co., Ltd.: CS150NX) was centrifuged by (rpm 3,000 rpm, separation time 30 minutes), the metal oxide particles ( after settling the a) (and metal oxide particles (a) adsorbed acrylic resin on the surface of (B)), the supernatant was removed, the sediment was concentrated to dryness. Results concentrated to dryness was sediment was analyzed by X-ray photoelectron spectroscopy (XPS), it was confirmed that there acrylic resin (B) on the surface of the metal oxide particles (A). That is, the surface of the metal oxide particles (A), acrylic resin (B) are adsorbed, adhered, the resulting particles (AB) acrylic resin surface of the metal oxide particles (A) (B) It was found to correspond to particles with.

Resin composition 1:
Resulting in an aqueous solvent, the particle (AB) and the acrylic resin (B), oxazoline compound (C 1 ') a is an oxazoline compound mixture of (1) was added in this order, mixed, the resin composition It was. (In the resin composition, particles (AB) and the acrylic resin (B), oxazoline compound (C 1 '), the mass ratio of, (AB) / (B) / (C 1') = 50/15/35 in is).

- oxazoline-based compound (1):
Methyl methacrylate: 50 parts by weight of ethyl acrylate: 25 parts by mass Styrene: 5 parts by weight of 2-isopropenyl-2-oxazoline: 20 parts by weight oxazoline group-containing resin composition obtained by copolymerizing the above composition, propylene glycol monomethyl ether and water mixed solvent (20/80 (weight ratio)) coating diluted in.

Laminated film was then sufficiently vacuum-dried PET pellets containing substantially no particles (intrinsic viscosity 0.63 dl / g), was melted in fed into an extruder 285 ° C., in a sheet from a T-die extrusion was cooled and solidified wound around a mirror surface cast drum having a surface temperature of 25 ° C. using a electrostatic casting method. The unstretched film was 3.4 times stretched in the longitudinal direction and heated to 90 ° C., and a uniaxially stretched film (B film).

It was then coated at a thickness of about 6μm using a bar coat the resin composition 1 corona discharge treated surface of the uniaxially stretched film. It led to a preheating zone width direction end portions of the uniaxially stretched film of the resin composition was applied by gripping with a clip, after the atmospheric temperature 75 ° C., followed by a 110 ° C. The ambient temperature using a radio instantiation heater, then ambient temperature as the 90 ° C., the resin composition was dried, yielding a resin layer. Subsequently continuously stretched 3.5 times in the width direction at 120 ° C. in the heating zone (stretching zone), followed by subjecting the 20 seconds heat treatment at 230 ° C. of heat treatment zone (thermal fixing zone), laminated completed in crystal orientation film It was obtained. The thickness of the PET film in the obtained laminated film 100 [mu] m, the thickness of the resin layer was about 0.02 [mu] m.

Characteristics of the resulting laminated film are shown in Table 1, Table 3. Initial low haze, high reflectance, transparency, visibility, initial adhesion is excellent, was excellent in wet heat adhesive property.
<Examples 2-4>
Oxazoline compound (C 1 '), oxazoline compound is a oxazoline compound (2) (Example 2), oxazoline compound c (Example 3), "EPOCROS" (registered trademark) WS-500 ((Co. ) manufactured by Nippon Shokubai) (except that the example 4), to obtain a laminated film in the same manner as in example 1.
- oxazoline-based compound (2):
Methyl methacrylate: 50 parts by weight of ethyl acrylate: 25 parts by mass Styrene: 5 parts by mass of 2-isopropenyl-5-ethyl-2-oxazoline: 20 parts by weight oxazoline group-containing resin composition obtained by copolymerizing the above composition, propylene glycol monomethyl paints diluted in a mixed solvent of ether and water (20/80 (weight ratio)).
- oxazoline-based compound (3):
Methyl methacrylate: 50 parts by weight of ethyl acrylate: 25 parts by mass Styrene: 5 parts by weight of 2-isopropenyl-2-oxazoline: 20 parts by weight oxazoline group-containing resin composition obtained by copolymerizing the above composition, propylene glycol monomethyl ether and water mixed solvent (20/80 (weight ratio)) coating diluted in.

The characteristics of the resulting laminated film are shown in Table 1. Compared to Example 1, by changing the type of oxazoline compound, the minimum reflectance is slightly lowered, although the initial haze is slightly higher is good, comparable transparency, initial adhesion, wet heat bonding sex, showed the visibility.
<Example 5>
Oxazoline compound (C 1 '), a melamine-based compound "NIKALAC" was changed to (R) MW12LF ((Ltd.) manufactured by Sanwa Chemical) may obtain a laminated film in the same manner as in Example 1 It was. The characteristics of the resulting laminated film are shown in Table 1. Compared to Example 1, it was changed to a melamine-based compound, the initial low haze, a high good reflectance, showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Example 6>
Oxazoline compound (C 1 '), a melamine compound is a melamine-based compound (1), except that the obtained a laminated film in the same manner as in Example 1.
Melamine compound (1):
"BECKAMINE" (registered trademark) APM (Dainippon Ink & Chemicals Co., Ltd.) was diluted with water paint.

The characteristics of the resulting laminated film are shown in Table 1, Table 3. Compared to Example 1, by changing the type of melamine-based compound, the minimum reflectance is slightly lowered, although the initial haze is slightly higher is good, comparable transparency, initial adhesion, wet heat bonding sex, showed the visibility.
<Examples 7-12>
In addition to the oxazoline-based compound (C 1 '), except that a melamine compound "NIKALAC" in combination with (R) MW12LF ((Ltd.) manufactured by Sanwa Chemical), changed the amount, as in Example 1 to obtain a laminated film method.

The characteristics of the resulting laminated film are shown in Table 1, Table 3. Compared to Example 1, by using both the melamine compound, reflectivity comparable, initial haze is low good transparency, initial adhesion, wet heat adhesive property, was excellent in visibility .
<Example 13>
Metal oxide particles (A), titanium oxide particles according to Table 1 "NanoTek" TiO 2 slurry (CI Kasei Co., number average particle diameter 20 nm) was changed to, as in Example 9 to obtain a laminated film in a way.

Compared to Example 9, by using a high refractive index titanium oxide particles, the initial haze comparable reflectance is slightly elevated good, comparable transparency, initial adhesion, wet heat adhesive property, It showed the visibility.
<Examples 14-16>
Metal oxide particles (A), FINEX-50 is a zinc oxide particle according to Table 1 (Sakai Chemical Industry Co., Ltd., number average particle diameter 20 nm) (Example 14), indium-doped tin oxide " NanoTek "ITO slurry (CI Kasei Co., Ltd., number average particle diameter 20 nm) (example 15), yttrium oxide" NanoTek "Y 2 O 3 slurry (CI Kasei Co., Ltd., number average particle diameter 20 nm) It was changed to (example 16), to obtain a laminated film in the same manner as in example 9.

Compared to Example 9, the initial haze slightly higher, is excellent despite the reflectance becomes slightly lower, transparency, wet heat adhesive property is good although visibility somewhat inferior, showed comparable initial adhesion It was.
<Example 17>
Except for changing the number-average particle diameter of the metal oxide particles (A) to 3nm it is to obtain a laminated film in the same manner as in Example 1.

Compared to Example 1, the initial haze slightly higher, is excellent despite the reflectance becomes slightly lower, although the initial adhesion to the laminate somewhat inferior, comparable transparency, wet heat adhesive property, the visibility Indicated.
<Examples 18-20>
Metal oxide number average particle diameter 15nm particles (A) (Example 18), 30 nm (Example 19), except for changing the 50 nm (Example 20), the laminated film in the same manner as in Example 1 Obtained.

Compared to Example 1, the initial haze comparable reflectance is good for those slightly lowered, showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Examples 21-22>
The addition amount of 20 parts by weight of the metal oxide particles (A) (Example 21), was changed to 30 parts by weight (Example 22), to obtain a laminated film in the same manner as in Example 1.

Compared to Example 1, equivalent initial haze is good shows the reflectivity showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Examples 23-24>
The addition amount of 50 parts by weight of the metal oxide particles (A) (Example 23), was changed to 70 parts by weight (Example 24), to obtain a laminated film in the same manner as in Example 1.

Compared to Example 1, a high initial haze somewhat, a good although the reflectance becomes slightly higher, although initial adhesion somewhat inferior showed comparable transparency, wet heat adhesive property, the visibility.
<Examples 25-27>
(Meth) acrylate monomer (b 1 '), n = 9 decyl methacrylate shown in Table 1 (Example 25), penta triacontyl methacrylate (Example 26) of n = 34, Nanodeshiru of n = 19 It was changed to methacrylate (example 27), to obtain a laminated film in the same manner as in example 1.

The characteristics of the resulting laminated film are shown in Table 2, Table 4. Compared to Example 1, equivalent initial haze is good shows the reflectivity showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Example 28>
(Meth) acrylate monomer (b 2 '), except for changing the isobornyl methacrylate having two hydrocarbon saturated ring, to obtain a laminated film in the same manner as in Example 1.

The characteristics of the resulting laminated film are shown in Table 2, Table 4. Compared to Example 1, equivalent initial haze is good shows the reflectivity showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Examples 29 to 32>
The addition amount of the acrylic resin (B), except for changing the addition amount described in Table 1 to obtain a laminated film in the same manner as in Example 1.

The characteristics of the resulting laminated film are shown in Table 2, Table 4. Compared to Example 1, by the amount of the acrylic resin (B) is reduced, the metal oxide particles (A) tends to agglomerate slightly, but the initial haze slightly increased, the reflectivity is slightly decreased It was good, showing comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Examples 33-34>
Resin composition 2 to 5
First, the resin composition 2-5 was adjusted as follows.

The resin composition 1, was added aqueous dispersion of fluorene copolymer polyester resin is a polyester resin (D) having a fluorene structure (D 1 aq), mixed to obtain a resin composition 2-5.

In the resin composition 2-5, the mass ratio of the particles (AB) and the acrylic resin (B), oxazoline compound (C 1 '), a polyester resin having a fluorene structure (D) are respectively as follows.

Resin composition 2: (AB) / (B ) / (C 1 ') / (D) = 50/15/35/5
The resin composition 3: (AB) / (B ) / (C 1 ') / (D) = 50/15/35/10
The resin composition 4: (AB) / (B ) / (C 1 ') / (D) = 50/15/35/20
Resin composition 5: (AB) / (B ) / (C 1 ') / (D) = 50/15/35/30
Under adjustment nitrogen gas atmosphere fluorene copolymerized polyester resin (D-1), dimethyl succinate 75 parts by mole as the dicarboxylic acid component not having a fluorene structure (Da 2), as the glycol component having a fluorene structure (Db 1) 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 80 molar parts, was charged ethylene glycol 20 parts by mole to the transesterification reactor as no glycol component a fluorene structure (Db 2), tetrabutyl thereto titanate (catalyst) was added 100 parts by weight with respect million parts by weight of the dicarboxylic acid ester derivative (dimethyl succinate), after 5 hours the esterification reaction at 160 ~ 200 ° C., to distill methanol. Further 240 ° C., for 30 minutes the reaction under a reduced pressure of 0.2 MPa, to obtain a polyester polyol.

Then the polyester polyol was charged with trivalent or higher-valent carboxylic acid component (Da 4) a is 1,2,4,5-benzene tetracarboxylic dianhydride 25 parts by mole, the reaction temperature 160 ~ 180 ° C. 3 It performs time reaction, to give a fluorene copolymerized polyester resin (D 1). Tg of the polyester resin was 99 ° C.. Incidentally, the copolymerization amount of glycol component having a fluorene structure fluorene copolymerized polyester resin (D 1) (Db 1), the amount and the total amount 100 mol% of the glycol component (Db) of the dicarboxylic acid component (Da) when a is 40 mol%. Furthermore, fluorene copolymerized polyester resin (D 1) is a polyester resin having no dicarboxylic acid component (Da 3) having a sulfonate group.
Fluorene copolymerized polyester resin (D 1) water dispersion (D 1 aq) adjusting said fluorene copolymerized polyester resin (D 1) with respect to 100 parts by weight, 532 parts by weight of water, 25 wt% ammonia water 2 parts, with the addition of 33 parts of butyl cellosolve was dissolved at 40 ° C.. Followed by sealing the reaction vessel, the internal temperature of the vessel was raised to 120 ° C. for 2 hours to obtain a water dispersion of the fluorene copolymerized polyester resin (D 1 aq). Aqueous dispersion of the fluorene copolymerized polyester resin composition of (D 1 aq) shown below.
Fluorene copolymerized polyester resin (D 1): 100 parts by weight water: 533 parts by weight of ammonia: 1 part by weight Butyl cellosolve: a 33 parts by weight of the resin composition, a resin containing a polyester resin (D) having a fluorene structure composition 2 (example 33), except for using the resin composition 3 (example 34), to obtain a laminated film in the same manner as in example 1.

Compared to Example 1, equivalent initial haze is good shows the reflectivity showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Examples 35-36>
As the resin composition, the resin composition 4 (Example 35) containing a polyester resin (D) having a fluorene structure, except for using the resin composition 5 (Example 36), in the same manner as in Example 1 to obtain a laminated film.

Compared to Example 1, the initial haze equivalent, reflectance is slightly higher good, comparable transparency, shows the initial adhesive property, was excellent wet heat adhesive property, the visibility.
<Examples 37-39>
(Meth) acrylate monomer (b 3 '), methacrylic acid having carboxyl groups (Example 37), N having a tertiary amino group, N- dimethylaminoethyl methacrylate (Example 38), butyl having a sulfonic acid group except that the acrylamide sulfonic acid (example 39), to obtain a laminated film in the same manner as in example 1.

The characteristics of the resulting laminated film are shown in Table 2, Table 4. Compared to Example 1, equivalent initial haze is good shows the reflectivity showed comparable transparency, initial adhesion, wet heat adhesive property, the visibility.
<Example 40>
Metal oxide particles (A), described in Table 1, a zirconium oxide particles of zirconium oxide dispersion SZR-CW (manufactured by Sakai Chemical Industry Co., Ltd., zirconium oxide particles: number average particle diameter 20 nm) and titanium oxide particles in a "NanoTek" TiO 2 slurry (CI Kasei Co., Ltd., number average particle diameter 20 nm) was changed to obtain a laminated film in the same manner as in example 9.

Compared to Example 9, by using a high refractive index titanium oxide particles, the initial haze comparable reflectance is slightly elevated good, comparable transparency, initial adhesion, wet heat adhesive property, It showed the visibility.
<Example 41>
Except for changing the film thickness 10nm is to obtain a laminated film in the same manner as in Example 17. Compared to Example 17, the initial low haze, reflectance significantly improved transparency, initial adhesive property, excellent visibility, showed comparable wet heat adhesive property.
<Comparative Example 1>
Except that the metal oxide particles (A) in Example 1, a silica particle "Snowtex" (registered trademark) CM (manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 20 nm) was changed to Example 1 to obtain a laminated film in the same manner as.

Compared to Example 1, by using silica particles, although the initial haze are equivalent, the reflectance is significantly reduced, transparency, initial adhesion, although wet heat adhesive property was good, visible It was those lacking in sex.
<Comparative Example 2-3>
The metal oxide particles (A) in Example 1, a MgF 2 particles "NanoTek" MgF 2 slurry (CI Kasei Co., Ltd., number average particle diameter 20 nm) (Comparative Example 2), is a hollow silica particles "Sururia" (registered trademark) TR112 was changed to (JGC catalysts and Chemicals Ltd., number average particle diameter 20 nm) (Comparative example 3) to obtain a laminated film in the same manner as in example 1.

Compared to Example 1, MgF 2 particles (Comparative Example 2), hollow silica particles (Comparative Example 3), by using, although initial haze are equivalent, the reflectance is significantly reduced, transparent sex, initial adhesiveness, but wet heat adhesive property was good, were those lacks visibility.
<Comparative Example 4-6>
Each particle diameter of the metal oxide particles (A) in Example 1, 2 nm (Comparative Example 4), 70 nm (Comparative Example 5), except for changing each 150 nm (Comparative Example 6), as in Example 1 in the method, to obtain a laminated film.

Compared to Example 1, by using the number-average particle diameter of 2 nm, 70 nm, the zirconium oxide particles of 150 nm, haze increases, reflectance decreases, transparency, initial adhesion, wet heat adhesive property, visible It was those lacking in sex.
<Comparative Example 7-8>
Instead of in Example 1 (meth) acrylate monomer (b 1 '), nonyl methacrylate (Comparative Example 7) of n = 8, except that n = 35 hexa triacontyl methacrylate (Comparative Example 8) was used as the to obtain a laminated film in the same manner as in example 1.

Compared to Example 1, nonyl methacrylate n = 8, n = 35 hex triacontyl acrylate of that were used, respectively, the metal oxide particles (A) is likely to agglomerate, transparency, initial adhesion , it was those that lack wet heat adhesive, to visibility.
<Comparative Example 9>
The (meth) acrylate monomer (b 2 '), except that the cyclopentanyl methacrylate having one cyclic structure, to obtain a laminated film in the same manner as in Example 1.

The characteristics of the resulting laminated film are shown in Table 2, Table 4. Compared to Example 1, by using cyclopentanyl methacrylate having one cyclic structure, metal oxide particles (A) is likely to agglomerate, transparency, initial adhesion, wet heat adhesive property, visibility It was those lacks.
<Comparative Example 10>
Except not using the oxazoline compound (C 1 '), thereby obtaining a laminated film in the same manner as in Example 1.

The characteristics of the resulting laminated film are shown in Table 2. Compared to Example 1, by not using the oxazoline compound, metal oxide particles (A) is likely to agglomerate, transparency, initial adhesion, wet heat adhesive property was achieved, lacks visibility.
<Comparative Example 11>
Except using no melamine compound (C 2 ') is to obtain a laminated film in the same manner as in Example 1.

The characteristics of the resulting laminated film are shown in Table 2, Table 4. Compared to Example 1, by not using the oxazoline compound, metal oxide particles (A) is likely to agglomerate, transparency, initial adhesion, wet heat adhesive property was achieved, lacks visibility.

Figure JPOXMLDOC01-appb-T000026

Figure JPOXMLDOC01-appb-T000027

Figure JPOXMLDOC01-appb-T000028

Figure JPOXMLDOC01-appb-T000029

The present invention, transparency, interference spots suppression at the time of laminating a high refractive index hard coat layer, excellent adhesiveness to the high refractive index hard coat layer, adhesion under high temperature and high humidity (wet heat adhesive property) laminated film relates, it is available to the optical easy adhesion film display applications.

Claims (14)

  1. A laminated film resin layer is provided on at least one side of the polyester film, the resin layer includes a number-average particle diameter of 3nm or more 50nm or less of the metal oxide particles (A), an acrylic resin (B), oxazoline system compound (C 1 ') and / or the melamine compound (C 2') contains at least, the acrylic resin (B), and monomer units (b 1) of the formula (1), formula (2 a monomer unit (b 2) represented by), the laminated film is a resin having a monomer unit represented by formula (3) (b 3).
    Figure JPOXMLDOC01-appb-C000001
    (In formula (1), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.)
    Figure JPOXMLDOC01-appb-C000002
    (Formula (In 2), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)
    Figure JPOXMLDOC01-appb-C000003
    In (formula (3), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
  2. A laminated film resin layer is provided on at least one side of the polyester film, the resin layer includes a number-average particle diameter of 3nm or more 50nm or less of the metal oxide particles (A), an acrylic resin (B), oxazoline system compound derived from components (C 1) and / or components derived from melamine compound (C 2) contains at least, the acrylic resin (B), monomer units (b 1 represented by the formula (1) ), a formula (2) monomer unit represented by (b 2), the laminated film is a resin having the formula (3) monomer unit represented by (b 3).
    Figure JPOXMLDOC01-appb-C000004
    (In formula (1), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.)
    Figure JPOXMLDOC01-appb-C000005
    (Formula (In 2), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)
    Figure JPOXMLDOC01-appb-C000006
    In (formula (3), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
  3. The metal oxide particles (A) are laminated film according to claim 1 or 2 particles having the acrylic resin (B) on the surface thereof.
  4. Laminate film according to the metal oxide particles (A) is any one of claims 1 to 3, titanium oxide particles (A 1 ') and / or zirconium oxide particles (A 2').
  5. The laminated film according to any one of claims 1 to 4, wherein the resin layer further contains a polyester resin (D) having a fluorene structure.
  6. Polyester resin having a fluorene structure (D) is 0 for the amount of the dicarboxylic acid component (Da) constituting the dicarboxylic acid component or not have (Da 3), or a polyester resin (D) having a sulfonate group the laminated film according to claim 5 having less than .1 mole%.
  7. The laminated film according to any one of the thickness of the resin layer, according to claim 1 to 6 is 10 ~ 50 nm.
  8. And at least manufacturing method of a multilayer film on one side to provide a resin layer of a polyester film, on at least one side of a polyester film, allowed to form a resin with the following resin composition and then, stretching the laminated film at least in a uniaxial direction and, then, the production method of the laminated film characterized in that a heat treatment to the laminated film.
    Here, the resin composition has a number-average particle diameter of 3nm or more 50nm or less of the metal oxide particles (A), an acrylic resin (B), oxazoline compound (C 1 ') and / or the melamine compound ( C2 ') with a least a resin composition containing, the acrylic resin (B), and monomer units (b 1) of the formula (1), a monomer unit represented by the formula (2) (b and 2) a resin having a monomer unit represented by formula (3) (b 3).
    Figure JPOXMLDOC01-appb-C000007
    (In formula (1), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.)
    Figure JPOXMLDOC01-appb-C000008
    (Formula (In 2), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)
    Figure JPOXMLDOC01-appb-C000009
    In (formula (3), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
  9. The acrylic resin (B) is represented by the formula (4) 'and, the formula (5) (meth) acrylate monomer (b 2 (meth) acrylate monomer (b1)' and), formula (12 ) is made resin is polymerized using represented (meth) acrylate monomer (b 3 '), the method for producing a laminated film according to claim 8.
    Figure JPOXMLDOC01-appb-C000010
    (In formula (4), R 1 group represents a hydrogen atom or a methyl group. Also n is an integer of 9 or more 34 or less.)
    Figure JPOXMLDOC01-appb-C000011
    (Formula (in 5), R 2 radical represents a hydrogen atom or a methyl group. Also, R 4 groups represent a hydrocarbon rings containing two or more groups of saturation.)
    Figure JPOXMLDOC01-appb-C000012
    In (Equation (6), R 3 radicals represents a hydrogen atom or a methyl group. Also, R 5 groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid It represents a group.)
  10. The metal oxide particles (A) is surface treated by said acrylic resin (B), method for producing a laminated film according to claim 8 or 9.
  11. The metal oxide particles (A) The method for producing a laminated film according to any titanium oxide particles (A 1 ') and / or zirconium oxide particles (A 2') of claims 8-10.
  12. Said resin composition, method for producing a laminated film according to any one of claims 8-11 containing a polyester resin having a fluorene structure (D).
  13. The polyester resin (D) is 0.1 mol% relative to the amount of either having no dicarboxylic acid component (Da 3), or dicarboxylic acid component constituting the polyester resin (D) (Da) having a sulfonate group method for producing a laminated film according to claim 12 having less than.
  14. Method for producing a laminated film according to any one of the dry thickness of the resin layer, formed by coating so that 10 ~ 50 nm claims 8-13.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016014085A (en) * 2014-07-01 2016-01-28 東レ株式会社 Laminated polyester film and production method thereof
JP2016169343A (en) * 2015-03-13 2016-09-23 住友大阪セメント株式会社 Composition containing inorganic particle, coating film, plastic substrate with coating film, and display device
JP2016194000A (en) * 2015-03-31 2016-11-17 住友大阪セメント株式会社 Inorganic particle-containing composition, coating film, plastic substrate with coating film, and display device
JP2017014479A (en) * 2015-07-03 2017-01-19 住友大阪セメント株式会社 Inorganic particle-containing composition, coated film, plastic substrate with coated film and display device
JP2017095734A (en) * 2015-11-13 2017-06-01 東洋紡株式会社 Laminated polyester film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000273272A (en) * 1999-03-25 2000-10-03 Jsr Corp Resin composition, its cured product and conjugated product
JP2007507342A (en) * 2003-05-20 2007-03-29 ディーエスエム アイピー アセッツ ビー.ブイ. An article comprising the method of coating the nanostructured surface, nanostructured coatings, and the coating
JP2011126162A (en) * 2009-12-18 2011-06-30 Toyobo Co Ltd Polyester film for molding and hard coat film for molding
JP2012128086A (en) * 2010-12-14 2012-07-05 Konica Minolta Advanced Layers Inc Hard coat film, and polarizer and liquid crystal display device using the same
JP2013052676A (en) * 2011-08-08 2013-03-21 Toray Ind Inc Optical laminate film

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4680204A (en) * 1983-09-06 1987-07-14 Ppg Industries, Inc. Color plus clear coating system utilizing inorganic microparticles
US4571363A (en) * 1983-12-12 1986-02-18 American Hoechst Corporation Polyester film primed with crosslinked acrylic polymers
US5021278A (en) * 1988-08-17 1991-06-04 General Motors Corporation Thermoformable multihued laminate films and processes
US5026448A (en) * 1989-04-03 1991-06-25 Reafler Gerald G Method of forming a glossy basecoat-clearcoat surface on a substrate
US5156904A (en) * 1990-05-18 1992-10-20 Hoechst Celanese Corporation Polymeric film coated in-line with polyethyleneimine
US5100735A (en) * 1990-07-25 1992-03-31 E. I. Du Pont De Nemours And Company Waterborne basecoat/high solids clear finish for automotive substrates having an improved appearance
DE4215499A1 (en) * 1992-05-12 1993-11-18 Basf Lacke & Farben A method for producing a multilayer protective and / or decorative coating on a substrate surface and for performing the method suitable aqueous paints
US6428738B1 (en) * 1995-11-01 2002-08-06 Patent Holding Company Method of manufacturing an in-mold laminate component
US6025449A (en) * 1997-03-05 2000-02-15 Kansai Paint Co., Ltd. Water-soluble acrylic resin, resin composition containing the same for use in water-based coating composition, water-based coating composition and coating method by use of the same
US6680104B2 (en) * 1998-03-27 2004-01-20 Leonard Kurz Gmbh & Co. Wrappable decorative film
AT332333T (en) * 1999-02-15 2006-07-15 Dsm Ip Assets Bv Resin composition and cured product
JP2000355086A (en) * 1999-06-15 2000-12-26 Mitsubishi Polyester Film Copp Coating film
JP2001240791A (en) * 2000-02-25 2001-09-04 Nippon Paint Co Ltd Method for forming composite coating film
US6794442B2 (en) * 2001-06-21 2004-09-21 Basf Corporation Fast drying basecoat refinish composition
US6822040B2 (en) * 2001-09-25 2004-11-23 Basf Corporation Basecoat composition with improved repair properties
JP4080756B2 (en) * 2002-02-01 2008-04-23 富士フイルム株式会社 Antireflection film and its manufacturing method, and an image display device
JP3904463B2 (en) * 2002-02-12 2007-04-11 サンノプコ株式会社 Automotive water-base paint composition
JP2005000787A (en) * 2003-06-11 2005-01-06 Nippon Bee Chemical Co Ltd Method of coating and finishing automobile body, and automobile body
US7794831B2 (en) * 2003-07-28 2010-09-14 Vampire Optical Coating, Inc. Anti-reflective coating
TWI378128B (en) * 2004-09-27 2012-12-01 Fujifilm Corp Coating composition, optical film, anti-reflection film, polarizing plate, and display unit using them
US20060165919A1 (en) * 2005-01-27 2006-07-27 Fuji Photo Film Co., Ltd. Coating composition, optical film, anti-reflection film, polarizing plate and image display device using the same
JP5116486B2 (en) * 2005-06-09 2013-01-09 関西ペイント株式会社 Method for forming a brilliant multi-layered coating film
US7641946B2 (en) * 2005-08-08 2010-01-05 Nitto Denko Corporation Adhesive film and image display device
TWI370152B (en) * 2005-09-27 2012-08-11 Nippon Catalytic Chem Ind
WO2009145075A1 (en) * 2008-05-28 2009-12-03 東レ株式会社 Laminated polyester film and antireflection film
EP2463316B1 (en) * 2009-08-04 2016-06-08 Idemitsu Kosan Co., Ltd. Acrylate composition
JP2011093290A (en) * 2009-09-30 2011-05-12 Toray Ind Inc Laminated polyester film
JP5853949B2 (en) * 2010-08-10 2016-02-09 東レ株式会社 Laminated polyester film and the optical laminate film using the same
CN103168057B (en) * 2010-10-25 2015-06-24 出光兴产株式会社 (Meth)acrylate composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000273272A (en) * 1999-03-25 2000-10-03 Jsr Corp Resin composition, its cured product and conjugated product
JP2007507342A (en) * 2003-05-20 2007-03-29 ディーエスエム アイピー アセッツ ビー.ブイ. An article comprising the method of coating the nanostructured surface, nanostructured coatings, and the coating
JP2011126162A (en) * 2009-12-18 2011-06-30 Toyobo Co Ltd Polyester film for molding and hard coat film for molding
JP2012128086A (en) * 2010-12-14 2012-07-05 Konica Minolta Advanced Layers Inc Hard coat film, and polarizer and liquid crystal display device using the same
JP2013052676A (en) * 2011-08-08 2013-03-21 Toray Ind Inc Optical laminate film

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016014085A (en) * 2014-07-01 2016-01-28 東レ株式会社 Laminated polyester film and production method thereof
JP2016169343A (en) * 2015-03-13 2016-09-23 住友大阪セメント株式会社 Composition containing inorganic particle, coating film, plastic substrate with coating film, and display device
JP2016194000A (en) * 2015-03-31 2016-11-17 住友大阪セメント株式会社 Inorganic particle-containing composition, coating film, plastic substrate with coating film, and display device
JP2017014479A (en) * 2015-07-03 2017-01-19 住友大阪セメント株式会社 Inorganic particle-containing composition, coated film, plastic substrate with coated film and display device
JP2017095734A (en) * 2015-11-13 2017-06-01 東洋紡株式会社 Laminated polyester film

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CN104159746A (en) 2014-11-19
TW201343396A (en) 2013-11-01
KR20140138643A (en) 2014-12-04
US20150086777A1 (en) 2015-03-26
TWI577553B (en) 2017-04-11
JP6070547B2 (en) 2017-02-01
CN104159746B (en) 2016-01-27
US9771491B2 (en) 2017-09-26

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